Solid electrolyte composition, solid electrolyte-containing sheet, all-solid state secondary battery, and methods for manufacturing solid electrolyte-containing sheet and all-solid state secondary battery

Patent metadata

Field	Value
Publication number	US-2019157715-A1
Application number	US-201916253481-A
Country	US
Kind code	A1
Filing date	Jan 22, 2019
Priority date	Jul 22, 2016
Publication date	May 23, 2019
Grant date	—

Abstract

Provided are a solid electrolyte composition containing an inorganic solid electrolyte, a specific fluorine-containing compound, and a dispersion medium, in which a content of the specific fluorine-containing compound in a total solid content of the solid electrolyte composition is 0.1% by mass or more and less than 20% by mass, a solid electrolyte-containing sheet having an inorganic solid electrolyte and a specific fluorine-containing compound, an all-solid state secondary battery, and methods for manufacturing a solid electrolyte-containing sheet and an all-solid state secondary battery.

First claim

1 . A solid electrolyte composition comprising: (A) an inorganic solid electrolyte having a conductivity of an ion of a metal belonging to Group I or II of the periodic table;
(B) a fluorine-containing compound satisfying all of the following conditions b1 to b4; and (C) a dispersion medium, wherein a content of the fluorine-containing compound (B) in a total solid content of the solid electrolyte composition is 0.1% by mass or more and less than 20% by mass, b1: as constituent atoms, a carbon atom and a fluorine atom are included, but a silicon atom is not included, b2: N F /N ALL that is a ratio of the number N F of fluorine atoms to the number N ALL of all atoms satisfies 0.10≤N F /N ALL ≤0.80, b3: a molecular weight is less than 5,000, which does not apply to a polymer, and b4: a boiling point at a normal pressure or an initiation temperature of thermal decomposition at a normal pressure exceeds 100° C., and wherein the fluorine-containing compound (B) is solid at a normal pressure and a normal temperature.

2 . The solid electrolyte composition according to claim 1 ,
wherein the fluorine-containing compound (B) has an aromatic ring.

3 . The solid electrolyte composition according to claim 1 ,
wherein the fluorine-containing compound (B) is at least one selected from compounds represented by any of Formulae (1) to (3),

in Formula (1), R 11 to R 13 each independently represent a fluorine-containing substituent or a hydrogen atom, X 11 to X 13 each independently represent a single bond, an alkylene group, —O—, —S—, —C(═O)—, —NR—, or a divalent linking group formed of a combination thereof, Y 11 to Y 13 each independently represent a single bond or an n-valent hydrocarbon group, m 11 to m 13 each independently represent an integer of 1 to 5, here, R represents a hydrogen atom or an alkyl group, n is m 11 +1, m 12 +1, or m 13 +1, in a case in which there is a plurality of R 11 's, the plurality of R 11 's may be identical to or different from each other, in a case in which there is a plurality of R 12 's, the plurality of R 12 's may be identical to or different from each other, and, in a case in which there is a plurality of R 13 's, the plurality of R 13 's may be identical to or different from each other, here, at least one of R 11 to R 13 represents a fluorine-containing substituent,
in Formula (2), a ring α represents a benzene ring or a naphthalene ring, R 21 represents a fluorine-containing substituent or a hydrogen atom, X 21 represents a single bond, an alkylene group, —O—, —S—, —C(═O)—, —NR—, or a divalent linking group formed of a combination thereof, Y 21 represents a single bond or an m 21 +1-valent hydrocarbon group, m 21 represents an integer of 1 to 5, n 21 represents an integer of 1 to 8, here, R represents a hydrogen atom or an alkyl group, R 22 represents an organic group, m 22 represents an integer of 0 to 7, in a case in which there is a plurality of R 21 's, the plurality of R 21 's may be identical to or different from each other, and, in a case in which there is a plurality of R 22 's, the plurality of R 22 's may be identical to or different from each other, here, at least one of R 21 's represents a fluorine -containing substituent,
in Formula (3), R 31 to R 36 each independently represent a fluorine-containing substituent or a hydrogen atom, X 31 to X 36 each independently represent a single bond, an alkylene group, —O—, —S—, —C(═O)—, —NR—, or a divalent linking group formed of a combination thereof, here, R represents a hydrogen atom or an alkyl group, and, here, at least one of R 31 to R 36 represents a fluorine-containing substituent.

4 . The solid electrolyte composition according to claim 3 ,
wherein the fluorine-containing substituent is a fluorine atom, a fluorine-substituted alkyl group, a fluorine-substituted alkoxy group, or a fluorine-substituted acyloxy group.

5 . The solid electrolyte composition according to claim 1 ,
wherein the dispersion medium (C) has a lower boiling point than the fluorine-containing compound (B).

6 . The solid electrolyte composition according to claim 1 ,
wherein the dispersion medium (C) is a hydrocarbon solvent.

7 . The solid electrolyte composition according to claim 1 , further comprising:
(D) a binder.

8 . The solid electrolyte composition according to claim 7 ,
wherein the binder (D) is polymer particles having a volume-average particle diameter of 10 nm to 30 μm.

9 . The solid electrolyte composition according to claim 1 ,
wherein the inorganic solid electrolyte having a conductivity of an ion of a metal belonging to Group I or II of the periodic table is a sulfide-based inorganic solid electrolyte (A).

10 . A solid electrolyte-containing sheet comprising:
(A) an inorganic solid electrolyte having a conductivity of an ion of a metal belonging to Group I or II of the periodic table; and (B) a fluorine-containing compound satisfying all of the following conditions b1 to b4, b1: as constituent atoms, a carbon atom and a fluorine atom are included, but a silicon atom is not included, b2: N F /N ALL that is a ratio of the number N F of fluorine atoms to the number N ALL of all atoms satisfies 0.10≤N F /N ALL ≤0.80, b3: a molecular weight is less than 5,000, which does not apply to a polymer, and b4: a boiling point at a normal pressure or an initiation temperature of thermal decomposition at a normal pressure exceeds 100° C., and wherein the fluorine-containing compound (B) is solid at a normal pressure and a normal temperature

11 . A method for manufacturing the solid electrolyte-containing sheet according to claim 10 , comprising:
a step of applying a solid electrolyte composition containing (A) the inorganic solid electrolyte having a conductivity of an ion of a metal belonging to Group I or II of the periodic table; (B) the fluorine-containing compound; and (C) a dispersion medium onto a base material; and a step of heating and drying the solid electrolyte composition.

12 . An all-solid state secondary battery comprising:
a positive electrode active material layer; a negative electrode active material layer; and a solid electrolyte layer, wherein at least one layer of the positive electrode active material layer, the negative electrode active material layer, or the solid electrolyte layer is the solid electrolyte-containing sheet according to claim 10 .

13 . A method for manufacturing an all-solid state secondary battery, comprising:
manufacturing a solid electrolyte-containing sheet by the manufacturing method according to claim 11 .

Assignees

• Fujifilm Corp

Inventors

• Makino Masaomi
• Mochizuki Hiroaki
• Yawata Toshihiko
• Mimura Tomonori

Classifications

• H01M10/052

  Li-accumulators · CPC title

• H01M4/0471

  involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis · CPC title

• H01B1/10

  sulfides · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M4/13

  Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof · CPC title